CN106795346A

CN106795346A - With the heterophasic polypropylene composition for improving impact strength/rigid balancing, improve powder flowbility, reduce discharge and low-shrinkage

Info

Publication number: CN106795346A
Application number: CN201580045830.9A
Authority: CN
Inventors: 王静波; 泡利·莱斯吉南; 托马斯·赫里; 马库斯·加莱特纳; 科奈利亚·泰宁戈; 卡尔海因茨·弗里德里希; 帕维尔·舒特沃
Original assignee: Borealis AS
Current assignee: Borealis AG; Borealis AS
Priority date: 2014-10-27
Filing date: 2015-10-16
Publication date: 2017-05-31
Anticipated expiration: 2035-10-16
Also published as: KR20170048597A; EP3212713B1; MX357096B; CA2964654C; WO2016066453A2; MX2017004539A; US20170240734A1; CA2964654A1; KR101802126B1; ES2713165T3; EA201700207A1; ES2713165T5; PL3212713T5; WO2016066453A3; JP6370483B2; EA033422B1; JP2017531721A; PL3212713T3; EP3212713B2; BR112017003454B1

Abstract

Heterophasic polypropylene composition and its purposes with the impact strength/rigid balancing for improving and with high fluidity, the discharge capacity for reducing and low-shrinkage.

Description

With improve impact strength/rigid balancing, improve powder flowbility, reduce discharge and The heterophasic polypropylene composition of low-shrinkage

Technical field

The present invention relates to there is the favourable impact strength for improving respectively/rigid balance and with powder flowbility high Heterophasic polypropylene composition.Additionally, heterophasic polypropylene composition has the discharge capacity of reduction and with low-shrinkage, therefore due to Its high polymer powder flowbility, while obtaining the improved stabilization of the polymerization for preparing heterophasic propylene composition Property.

Moreover, it relates to the product being made up of polypropene composition of the invention, particularly membrane product, extrusion system Product, blow molded article or injection molded article.Finally, the invention further relates to polypropene composition of the invention and described group Compound is preparing membrane product, extruded product, blow molded article or injection molded article (such as with the combination of filler or reinforcing agent The component of pouch and bag, pipe and accessory, transportation package holdses and automobile exterior and interior trim, such as instrument board, door covering, operation Platform, bumper and decoration) in purposes.

Background technology

Polymer, such as polypropylene, are increasingly being used in the application of different requirements.Meanwhile, to meeting these applications The polymer of customization of requirement be also carried out lasting research.Because the property of many polymer is direct or indirect correlation , that is, improving particular characteristic can only be completed with sacrificing another property as cost, therefore these requirements are challenging.Can be with For example improve rigidity by increasing the crystallinity and/or relative quantity of homopolymers in composition.As a result, material becomes more It is crisp, so as to cause poor impact property.It is known to be gathered so as to obtain out-phase by the way that rubber is mutually dispersed in polymeric matrix Propylene compositions improve polyacrylic impact strength.

This heterophasic propylene copolymer includes the matrix for Noblen or atactic propene copolymer, common in heterophasic propylene The amorphous phase comprising propylene copolymer rubbers (elastomer) is dispersed with polymers.Therefore, it not is matrix that polypropylene matrix is included Part (fine) scattered field trash, and the field trash include elastomer.Term field trash represents matrix and is mingled with Thing forms different phases in heterophasic propylene copolymer, and the field trash is for example by high resolution microscope (such as electronic display Micro mirror or scanning force microscopy or AFM) or it is visible by dynamic mechanical analysis (DMTA).Additionally, out-phase is poly- Propylene can to a certain extent include crystalline polyethylene, and it is the side reaction product for preparing heterophasic propylene copolymer and obtaining. Due to thermodynamic one, this crystalline polyethylene exists as the field trash of amorphous phase.

One of this heterophasic polypropylene composition preferably application be its purposes in automobile application field, this be due to Replace the trend of metal parts with plastics, i.e., especially needing to be replaced with lighter plastics can undergo such as -30 DEG C or -40 DEG C extremely low The automobile component that temperature is still made up of metal alloy.

Additionally, especially needing the out-phase material of high fluidity in automotive field.

Powder flowbility, i.e., the non-sticky of aggregated powder, for out-phase High impact polypropylene group prepared by reactor Compound (RTPO) is especially important, and wherein polypropylene homopolymer (homopolymerization PP) matrix and the rubber as dispersed phase are to employ string Prepared in the multi-stage method of multiple reactors of connection.

During the course of the reaction, in the hole and hole of the particle formed in the first stage that rubber is in multistage polymerization.When When hole and hole in homopolymerization PP matrix are completely filled, extra rubber starts to surface migration, result between particle The viscosity of sticky (causing particle aggregation) and particle and reactor wall between.Which results in the serious problems in the method.

Additionally, at present, Polymer processors need the material with low-emission to meet regulator and consumer Sustainable growth demand.

Another of acrylic resin has the disadvantage, in most forming methods, they experience obvious shaping after-contraction.This Mean in the application that dimensional tolerance is important, it is necessary to according to specific composition and specific forming operation come custom mold Tool, with the component end item of the accurate dimension needed for producing.This contraction problem is particularly troublesome, and it is specific group that manufacturer has Compound and the mould of forming operation customization, and subsequently desire to replace different composition or to limit the method cold for example to improve But speed.Because acrylic resin shows difference in shrinkage in the longitudinal and transverse direction after shaping, make the problem tighter Weight.

Although substantial amounts of development has been carried out in heterophasic polypropylene compositions field, up to the present do not have also Have find with powder flowbility high, low-emission and low-shrinkage be combined on impact strength and rigid well balanced Polymer composition.

Therefore, there is still a need for having and low-emission and lower shrinkage while the impact resistance of acceptable (low temperature) is kept High rigidity and the heterophasic polypropylene composition of powder flowbility high that rate is combined.

It is therefore an object of the present invention to provide such material.

The content of the invention

The present invention based on the finding that：Above-mentioned purpose can be realized by specific heterophasic polypropylene composition, the combination Thing includes：

(A) the crystalline isotactic propylene homopolymer matrix of 48 to 78 weight %, it has and passes through¹³C-NMR spectroscopic assays Five unit group concentration more than 96 moles of % and according to ISO 1133 determined under 230 DEG C and 2.16kg loads 15 to Matrix melt flow rate (MFR) (MFR in the range of 200g/10min_M),

(B) 22 to 52 weight % predominantly unbodied propylene copolymer, its have 25 to 48 weight % ethene and/ Or with 4 to 10 alpha-olefins of carbon atom, be present in composition as scattered particle, and

(C) crystalline ethylene copolymer of 0.0 to 5.0 weight %, it has 3 to 10 alpha-olefins of carbon atom, used as (B) The field trash of discrete particles be present in composition, and

(D) α-phase and/or the α nucleators of γ-phase for isotactic polypropylene of 0 to 1.0 weight %,

The composition is further characterized in that

Always being melted according to what ISO 1133 was determined under 230 DEG C and 2.16kg loads in the range of (i) 2.0 to 50g/10min Body flow rate (MFR_T),

(ii) the xylene soluble part fraction determined at 25 DEG C according to ISO 16152 in the range of 22 to 52 weight % (XCS),

(iii) being determined in 135 DEG C of naphthalane according to DIN ISO 1628/1 in the range of 2.5 to 9.0dl/g The inherent viscosity of XCS fractions, and

(iv) relative amount (I of the isolated ethene sequence pair block ethylene sequence of the XCS fractions of inequality (I) is met (E))

I(E)<78–1.97×C+0.015×(C)²

Wherein C is the co-monomer content [weight %] of XCS fractions

Wherein I (E) contents by etc. formula (II) defined,

Wherein

I (E) is the relative amount [%] of isolated ethene sequence pair block ethylene sequence；

FPEP is the molar fraction of propylene/ethylene/propylene sequences (PEP) in sample；

FPEE be in sample propylene/ethylene/ethene sequence (PEE) and ethylene/vinyl/propylene sequences (EEP) mole point Number；

FEEE is the molar fraction of ethylene/vinyl/ethene sequence (EEE) in sample；

Wherein all sequences concentration is all based on¹³The unit group analysis of statistics three of C-NMR data.

The summation of the percentage of each component of composition is equal to 100%.

The combination of the particularly specific combination and its property of component (A) and (B) is generated with performance is improved, and is such as improved Impact strength/rigidity balance, powder flowbility high, reduce discharge capacity and low-shrinkage composition.Additionally, particularly high Powder flowbility causes the stability of the improvement of the polymerization for preparing heterophasic propylene composition.

In first embodiment of the invention, heterophasic polypropylene composition is free of phthalate and they are each From catabolite, it is preferable that heterophasic polypropylene composition is produced without phthalic compounds and its their own decomposition Thing.

According to the present invention, term " phthalic compounds " refers to phthalic acid (CAS 88-99-3), itself and fat The monoesters class and two esters and phthalic anhydride of fat race, alicyclic and aromatics alcohols.

On the other hand, membrane product, extruded product, blow molded article or note are being prepared the present invention relates to the composition Penetrate moulded products (component of such as pouch and bag, pipe and accessory, transportation package holdses and automobile exterior and interior trim, such as instrument Plate, door covering, operating desk, bumper and decoration) in purposes.

In this regard, composition of the invention can also be used with filler or reagents recombination.

On the other hand, the present invention relates to by polypropene composition of the invention or by the composition and filler or enhancing The product that the combination of agent is made, particularly membrane product or extruded product, blow molded article or injection molded article.

Specific embodiment

Each component is defined more fully below.

Specific heterophasic polypropylene composition of the invention at least includes component (A) and component (B).

Component (A)：

The component (A) of the specific heterophasic polypropylene composition is that the crystallization of the matrix to form heterophasic polypropylene composition is entirely same Vertical structure Noblen.

Term homopolymers used in the present invention be related to by substantially, i.e. at least 97 weight %, be preferably at least 98 weights The polypropylene of the propylene units composition of amount %, more preferably at least 99 weight %, still more preferably at least 99.8 weight %.Excellent In the embodiment of choosing, it is detectable there was only propylene units in Noblen.

Propylene homopolymer matrix is isotactic, with the group concentration of Unit five high, i.e., higher than 96 moles of Unit five of % Group concentration, such as at least 96.3 moles five unit group concentration of %.Five unit group concentration are preferably 96.5 moles of % to 99.9%, more Preferably 96.7 moles % to 99.8%.

The melt flow rate (MFR) MFR of propylene homopolymer matrix₂(ISO 1133；230℃；2.16kg) in 15 to 200g/ In the range of 10min, preferably in the range of 17 to 170g/10min, more preferably in the range of 18 to 150g/10min.

The MFR of matrix₂It is referred to as matrix melt flow rate (MFR) (MFR_M)。

Moreover it is preferred that the amount of the xylene soluble part of propylene homopolymer matrix is not too high.Xylene soluble part is The solvable polymer moieties in cold xylene, it is by the dissolving in the dimethylbenzene of boiling and by undissolved part from cooling Crystallize to determine in solution (being determined at 25 DEG C according to ISO 16152).Xylene soluble part fraction includes low stereospecificity Polymer chain, and characterize amorphous regions amount.It is preferred, therefore, that the xylene soluble part level of propylene homopolymer matrix Divide in the range of 0.5 weight of weight % to 5.0 %, more preferably in the range of 0.7 weight of weight % to 4.5 %.Even In further preferred embodiment, xylene soluble part fraction is in the range of 0.8 weight of weight % to 4.0 %.

Noblen has the melt temperature T determined by dsc analysis according to ISO 11357_m1With melting enthalpy H_m1。

Preferably, the T of Noblen_m1In the range of 160 DEG C to 170 DEG C, more preferably in 161 DEG C to 169 DEG C of model In enclosing, most preferably in the range of 162 DEG C to 168 DEG C.

Preferably, the H of Noblen_m1In the range of 70 to 100J/g, more preferably in the range of 70 to 95J/g, Most preferably in the range of 70 to 92J/g.

Propylene homopolymer matrix can be unimodal or multimodal, as bimodal.

Preferably, the propylene homopolymer matrix is multimodal, particularly bimodal.

On unimodal and multimodal (such as bimodal) definition, definition hereafter is refer to.

When propylene homopolymer matrix includes two or more different acrylic polymers, they can be with different monomers Composition and/or the polymer with different molecular weight distribution.These components can have identical or different monomer composition and stand Structure regularity.

When it is unimodal that propylene homopolymer matrix is in molecular weight distribution, it can be prepared by single-stage process, For example, slurry or gas phase process in slurry or Gas-phase reactor.Preferably, unimodal matrix is gathered as slurry polymerization Close.Alternatively, unimodal matrix can be prepared by multi-stage method, and being used in every stage method causes similar polymer property Method condition.

If propylene homopolymer matrix has multimodal or double-hump characteristics, can be by by different polymer types, i.e., not Propylene homopolymer matrix is prepared with the polymer blending of molecular weight and/or co-monomer content.But in this case, it is excellent Choosing, the polymers compositions of polypropylene matrix is the reactor of arranged in series to be used in consecutive steps method and different Operate to prepare under reaction condition.Therefore, each grade of branch for being prepared in particular reactor has its respective molecular weight Distribution and/or co-monomer content distribution.

When by the superposition of the distribution curve (molecular weight or co-monomer content) of these fractions with obtain final polymer point Son amount distribution curve or co-monomer content distribution curve when, these curves can show two or more maximum or when with it is each The curve of individual fraction shows when being compared and at least substantially broaden.According to the quantity of step, in two or more continuous steps This polymer prepared in rapid is referred to as bimodal or multimodal.

Component (B)

The component (B) of the specific heterophasic polypropylene composition is predominantly amorphous propene copolymer, and it is used as dispersion Grain is present in composition.(i.e. dispersed phase)

Suitable comonomer for propylene copolymer is ethene and/or with 4 to 10 alpha-olefins of carbon atom.

Suitable C₄-C₁₀Alpha-olefin be 1- butylene, 1- amylenes, 1- hexenes, 1- heptene and 1- octenes.

Preferably, component (B) is the copolymer of propylene and ethene.

The amount of ethene is in the range of 25 to 48 weight % in component (B), preferably in the range of 26 to 46 weight %, more It is preferred that in the range of 27 to 45 weight %.

As propylene homopolymer matrix, dispersed phase can be unimodal or multimodal, as bimodal.

In one embodiment, dispersed phase is unimodal.More specifically, in view of inherent viscosity and/or comonomer point Cloth, the dispersed phase is preferably unimodal.On unimodal and multimodal (such as bimodal) definition, above-mentioned definition is refer to.

Component (C)

It is optionally present as the crystalline ethylene copolymer with 3 to 10 alpha-olefins of carbon atom of component (C).

Alpha-olefin with 3 to 10 carbon atoms is, for example, propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene and 1- pungent Alkene.

Crystalline ethylene copolymer is the side reaction product for preparing heterophasic polypropylene composition and obtaining.Because thermodynamics is former Cause, the crystalline ethylene copolymer is present in amorphous phase as field trash.

Crystalline ethylene copolymer has the melt temperature T determined by dsc analysis according to ISO 11357_m2And melting enthalpy H_m2。

Preferably, the T of crystalline ethylene copolymer_m2In the range of 105 DEG C to 130 DEG C, more preferably at 110 DEG C to 127 DEG C In the range of, most preferably in the range of 112 DEG C to 124 DEG C.

Preferably, the H of crystalline ethylene copolymer_m2Less than 7J/g, more preferably less than even more preferably less than 6J/g, 5J/g.

Component (D)

It is optionally present as the α nucleators for α-phase and/or the isotactic polypropylene of γ-phase of component (D).

It is well known that different types of crystal nucleating agent will differently influence the crystal structure of polymer, increase complete With the vertical polyacrylic specific crystal formation of structure (such as α-crystal formation of monocline, the beta-crystal of accurate six side and orthogonal γ-crystal formation) presence and Relative quantity.

Although polymer architecture will influence the performance degree of specific nucleation, the type of the crystal for being formed will be by nucleator Determine.

α-nucleator (D) (if present) generally with 0.0001 to 1.0 weight %, be preferably 0.0005 to 0.8 weight %, More preferably a small amount of addition of 0.001 to 0.5 weight %.

α-nucleator (D) can be polyacrylic monocline α-crystal formation and/or orthogonal γ-crystal formation nucleator it is any Compound.

In general, two class α-nucleator, i.e. particulate nucleants and soluble nucleator can be distinguished.

Particulate nucleants show conventional dispersion mechanism, and wherein granularity and the polarity difference to polymer is decisive 's.Such example is inorganic nucleator, such as talcum, also organic nucleating agent, such as Sodium Benzoate, organic phosphate and to uncle The salt of butylbenzoic acid, and polymerization nucleator, such as vinyl compound (the such as polyvinyl eyclohexane or polytetrafluoro of polymerization Ethene).Further detail below on these nucleators can be found in such as WO 99/24479 and WO 99/24501.

Soluble nucleator be have heating when dissolving and cooling when recrystallize order define decentralization into Core agent.In the case of the latter, solubility and resulting crystal shape are conclusive for efficiency.This kind of example be as Glucitol derivative (such as two (alkylbenzylidene) glucitols, such as 1,3:2,4-25 dibenzyl sorbitols, 1,3:2,4 2 (4- methylbenzilidenes) sorbierite, 1,3:2,4- bis- (4- ethylbenzylidenes) sorbierite and 1,3:2,4- is double, and (3,4- dimethyl is sub- Benzyl) sorbierite) and (such as deoxidations -4,6 of 1,2,3- tri- of promise Buddhist nun 01 derivatives:Double-the O- [(4- propyl group phenyl) methylene] of 5,7- Promise Buddhist nun alcohol) and benzene-trigalloyl amine (such as 1,3,5- benzene trigalloyl amines of substitution, such as N, N', N "-three-tert-butyl group -1,3,5- benzene three - three-cyclohexyl of carboxylic acid amides, N, N', N " -1,3,5- benzene-tri carboxylic acid amide and N- [3,5- couples-(2,2- dimethyl-propiono ammonia Base)-phenyl] -2,2- dimethvl-propionamides) and nucleator.

However, in the case where heterophasic polypropylene composition includes α-nucleator, heterophasic polypropylene composition preferably has There is the crystallization temperature higher than the crystallization temperature of non-nucleation heterophasic polypropylene composition, dsc analysis are passed through thus according to ISO 11357 Determine, the crystallization temperature of the heterophasic polypropylene composition of nucleation is higher than 120 DEG C.

Heterophasic composition

Heterophasic polypropylene composition of the invention is further characterized in that in the range of 2.0 to 50g/10min, preferably exists In the range of 2.5 to 45g/10min, more preferably in the range of 3.0 to 40g/10min, even more preferably in 3.5 to 35g/ Total melt flow rate (MFR) (MFR in the range of 10min_T)(ISO 1133；230℃；2.16kg).

The ratio of total melt flow rate (MFR) of heterophasic polypropylene composition and the melt flow rate (MFR) of propylene homopolymer matrix MFR_T/MFR_MIt is≤0.5.

Preferably, ratio MFR_T/MFR_MIn the range of 0.05 to 0.45, more preferably in the range of 0.07 to 0.40.

Dimethylbenzene cold DDGS (XCS) fraction according to (25 DEG C) measure of ISO 16152 of heterophasic polypropylene composition exists In the range of 22.0 to 52.0 weight %, preferably in the range of 23.0 to 50.0 weight %, more preferably in 24.0 to 45.0 weights In the range of amount %.

However, it should be understood that the dimethylbenzene of heterophasic polypropylene composition cold DDGS (XCS) fraction is glued by its characteristic Degree is illustrated.

For the present invention, it should be appreciated that the cold DDGS fraction (XCS) of dimethylbenzene of heterophasic polypropylene composition has To less than 7.0dl/g in the range of 2.5 to 9.0dl/g, preferably in the range of 2.6 to 8.5dl/g, more preferably 2.7 In the range of according to ISO 1628/1 (at 135 DEG C in naphthalane) determine inherent viscosity (iV).

Another requirement to dimethylbenzene cold DDGS (XCS) fraction of heterophasic polypropylene composition is isolated ethene sequence To the certain content (I (E)) of block ethylene sequence.

I (E) contents by etc. formula (II) defined,

Wherein

FEEE is the molar fraction of ethylene/vinyl/ethene sequence (EEE) in sample

I (E) content can also be referred to as normalized PEP values (nPEP), and it must is fulfilled for inequality (I)：

I(E)<78–1.97×C+0.015×(C)²

Wherein C is the co-monomer content of XCS fractions, preferably ethylene contents [weight %].

It is further preferred, that the comonomer of the dimethylbenzene of heterophasic polypropylene composition cold DDGS (XCS) fraction contains Measure, be preferably ethylene contents in the range of 26.0 to 50.0 weight %, preferably in the range of 30.0 to 48.0 weight %, and More preferably in the range of 35.0 to 47.0 weight %.

The comonomer being present in dimethylbenzene cold DDGS (XCS) fraction is above to propylene copolymer (component B) Defined those fractions.In a preferred embodiment, comonomer is only ethene.

It is to be further understood that in whole heterophasic polypropylene compositions, the total content of comonomer (ethene and has The 4-10 summation of the content of the alpha-olefin of carbon atom) it is quite moderate.

It is preferred, therefore, that the total comonomer content of heterophasic polypropylene composition, be preferably ethylene contents 6.0 to In the range of 26.0 weight %, preferably in the range of 6.5 to 25.0%, more preferably in the range of 7.0 to 24.0 weight %.

Additionally, heterophasic polypropylene composition of the invention has at least the first glass transition temperature T_gAnd the second glass (1) Glass transition temperature T_g(2), wherein the first glass transition temperature T_g(1) higher than the second glass transition temperature T_g(2)。 Glass transition temperature T_gIt is to be determined by dynamic mechanical analysis (DMTA) according to ISO 6721-7.

Therefore, heterophasic polypropylene composition has the first glass transition temperature T in the range of -4 to+4 DEG C_g(1) and/ Or the second glass transition temperature T in the range of -65 to -35 DEG C_g(2)。

The heterogeneous structure (being mainly dispersed in the amorphous propene copolymer in matrix) of heterophasic polypropylene composition can be with Determined by the presence of at least two different glass transition temperatures.First glass transition temperature (T higher_g(1)) Expression matrix, i.e. crystalline polypropylene homopolymer, and the second relatively low glass transition temperature (T_g(2) heterophasic polypropylene group) is reflected The predominantly unbodied propylene copolymer of compound.

Preferably, the first glass transition temperature T_g(1) in the range of -3 to+3 DEG C, more preferably in -2 to+2 DEG C of model In enclosing.

Second glass transition temperature T_g(2) preferably in the range of -58 to -37 DEG C, more preferably at -57 to -38 DEG C In the range of.

Heterophasic polypropylene composition of the invention have less than 20 seconds, be preferably less than 18 seconds according to ISO 6186: The favourable powder flowbility high of the powder flowbility test measurement of 1998, method A.

According to VDA 277:The total release of the volatile matter of the 1995 heterophasic polypropylene compositions of the invention for determining is less than 25ppm, preferably shorter than 20ppm.

The part being made up of heterophasic polypropylene composition of the invention has low-shrinkage in the vertical.Preferably, longitudinal direction On shrinkage factor be less than 1.2%, specifically lower than 1.1%.

Shrinkage factor is measured described in following article " assay method explanation ".

According to ISO 178 in 80 × 10 × 4mm³Injection moulding sample on measure, heterophasic polypropylene of the invention combination Thing has in the range of 500 to 1100MPa, preferably in the range of 600 to 1050MPa, more preferably in 650 to 1020MPa scopes Interior bending modulus (FM).

Alternatively, (crosshead speed 1mm/min) measurement, out-phase of the invention poly- third at 23 DEG C according to ISO 527-1 Ene compositions have in the range of 500 to 1100MPa, preferably in the range of 600 to 1050MPa, more preferably 650 to Stretch modulus (TM) in the range of 1020MPa.

Measured at 23 DEG C according to ISO 179-1eA, the simply supported beam notch impact strength of the heterophasic polypropylene composition is At least 10.0kJ/m², it is therefore preferred in 12.0 to 100kJ/m²In the range of, preferably in 14.0 to 95.0kJ/m²Scope It is interior, more preferably in 15.0 to 90.0kJ/m²In the range of.

Measured at -20 DEG C according to ISO 179-1eA, the simply supported beam notch impact strength of the heterophasic polypropylene composition exists 4.5 to 35.0kJ/m²In the range of, preferably in 5.0 to 32.0kJ/m²In the range of, more preferably in 5.5 to 30.0kJ/m²Model In enclosing.

In preferred embodiments, the heterophasic polypropylene composition is preferably free of phthalate and they are each From catabolite, that is, the inside donor of the Ziegler-Natta catalyst for being commonly used as preparing heterophasic polypropylene composition Phthalate.Preferably, heterophasic polypropylene composition is free of phthalic compounds and their own point Solution product, i.e., usually as Ziegler-Natta catalyst inside donor phthalic compounds.

Term " is free of " phthalate, preferably phthalic compounds, and meaning in the present invention refers to Heterophasic polypropylene composition, can't detect phthalate from Ziegler-Natta catalyst and corresponding wherein Catabolite, preferably can't detect phthalic compounds and corresponding catabolite.

Heterophasic polypropylene composition of the invention is made up of component (A) and (B) and optional component (C) and (D).

Component (A) exists with 48 to 78 weight %, the amount of preferably 46 to 76 weight %, more preferably 45 to 75 weight %.

Component (B) exists with 22 to 52 weight %, the amount of preferably 25 to 52 weight %, more preferably 26 to 50 weight %.

Component (C) is deposited with 0 to 5.0 weight %, preferably 0.1 to 4.0 weight %, the amount of more preferably 0.2 to 3.0 weight % .

Component (D) exists with 0 to 1.0 weight %, the amount of preferably 0 to 0.8 weight %, more preferably 0 to 0.5 weight %.

According to the presence of other fractions or additive, the summation of fraction (A), (B), (C) and (D) is 100 weight % or low In 100 weight %.According to the present invention, the scope of percentage by weight (weight %) used herein defines each fraction or component Amount based on whole heterophasic polypropylene composition.It is 100 weight that all fractions and component have altogether.

According to the present invention, in addition to polymers compositions and α-nucleator (D), the heterophasic polypropylene composition can include Other non-polymeric ingredients, additive for example for various purposes.

The following is optional additive：It is technique and heat stabilizer, the pigment and other colouring agents that keep transparency, anti-oxidant Agent, antistatic additive, slip agent, UV stabilizer, acid scavenger.

According to the type of additive, the weight that can be based on heterophasic polypropylene composition adds 0.001 to 2.0 weight %'s These additives of amount.

If heterophasic polypropylene composition of the invention is used with filler or reagents recombination, based on total combination Thing, filler or reinforcing agent exist with the amount less than 30 weight %, preferably shorter than 25 weight %, more preferably less than 22 weight %.

Suitable filler used includes but is not limited to talcum, calcium carbonate, chalk, viscous in polypropene composition of the invention Soil, kaolin, silica, pyrogenic silica, mica, wollastonite, feldspar, alumina silicate, calcium silicates, aluminum oxide, such as The hydrated alumina of hibbsite, glass microsphere, ceramic microsphere, wood powder, marble powder, magnesia, magnesium hydroxide, oxidation Antimony, zinc oxide, barium sulfate and titanium dioxide.

The example of reinforcing agent used includes but is not limited to mineral fibres, glass fibers in polypropene composition of the invention Dimension, carbon fiber and natural or synthetic organic fiber.

The preparation of heterophasic polypropylene composition

The heterophasic polypropylene composition can be made in the multi-stage method including at least three reactors being connected in series It is standby, wherein preparing polypropylene homopolymer matrix (A) first, and in a subsequent step, third is prepared in the presence of matrix (A) Alkene copolymer (B) prepares third after they are polymerized by the way that matrix polymer (A) and propylene copolymer (B) are blended Alkene copolymer (B).

The further possibility for preparing heterophasic polypropylene composition of the invention will be connected in series including at least three The heterophasic polypropylene composition prepared in the multi-stage method of reactor enters with the polypropylene homopolymer matrix (A) of specific additional quantity Row is blended to realize the target capabilities of XCS fractions, prepares polypropylene homopolymer matrix (A) first in multi-stage method, and In a subsequent step, propylene copolymer (B) is prepared in the presence of matrix (A).

In a preferred embodiment, to prepare polypropylene in a slurry-phase reactor and subsequent Gas-phase reactor equal Copolymer matrix (A), then prepares propylene copolymer (B) at least one other Gas-phase reactor.

Therefore, the present invention can be generally prepared at least 3 reactors of the cascade with the 4th optional reactor Heterophasic polypropylene composition, wherein first reactor is fluid bulk reactor, preferably circulation type design fluid bulk Reactor, and all subsequent reactors are Gas-phase reactor, the preferably Gas-phase reactor of design of Fluidized bed.

Preferably, the component for being prepared in the first two reactor is crystallizable Noblen (acquisition matrix), and The component prepared in 3rd reactor is the predominantly unbodied copolymer with higher comonomer amount.It is optionally possible to Other components are prepared in the 4th reactor, it is also predominantly unbodied copolymer or crystalline ethylene homopolymers or copolymerization Thing.

Work as polypropene composition, i.e. heterophasic polypropylene composition, three or four polymer reactors (R1), (R2), (R3) in the case of and being prepared in optional (R4), the matrix (A) of polypropene composition, i.e. polypropylene homopolymer are anti-in polymerization Answer in device (R1) in (such as in slurry-phase reactor (SR1), such as in circulating reactor (LR1)) and polymer reactor (R2) (such as in Gas-phase reactor (GPR-1)) is prepared, and predominantly unbodied copolymer (B) is in polymer reactor (R3) (such as in optional Gas-phase reactor in (such as in Gas-phase reactor (GPR-2)) and optional polymer reactor (R4) (GPR-3) in) it is prepared.

Preferably,

A () polypropylene in first reactor obtains the first Noblen fraction,

B be transferred to the first Noblen fraction in second reactor by (),

C () in the presence of the first Noblen fraction, be polymerized other propylene in the second reactor, obtains Second Noblen fraction, the first Noblen fraction and the second Noblen fraction form matrix (A),

D be transferred to described matrix (A) in the 3rd reactor by (),

E () is in the presence of matrix (A) by propylene and ethene and/or C in the 3rd reactor₄-C₁₀Alpha-olefines polymerization Close, obtain predominantly unbodied propylene copolymer (B), described matrix (A) and the predominantly unbodied propylene copolymer (B) heterophasic polypropylene composition is formed.

In another preferred pattern, the 3rd Gas-phase reactor is used, therefore the method is further comprising the steps of：

F composition that () will obtain in step (e) is transferred to the 4th reactor, and

In the presence of g heterophasic polypropylene composition that () obtains in the 4th reactor fraction, in the 4th reactor It is middle by propylene and ethene and/or C₄To C₁₀Alpha-olefin is polymerized, and obtains another predominantly unbodied propylene copolymer (B), Another predominantly unbodied propylene copolymer (B) forms final together with the heterophasic polypropylene composition of step (e) Heterophasic polypropylene composition.

As described above, by using arranged in series and the circulating reactor and at least one that works at different conditions Gas-phase reactor, can obtain the propylene homopolymer matrix (A) of multimodal (such as bimodal).

First reactor is preferably slurry-phase reactor and can be operate in any body or slurry continuous or simple The batch stirred tank reactor or circulating reactor of stirring.Body refers to including at least 60% (w/w) monomer Reaction medium in polymerization.According to the present invention, slurry-phase reactor is preferably (body) circulating reactor.

Second reactor, the 3rd reactor and the 4th optional reactor are preferably Gas-phase reactor.This gas phase is anti- It can be any mechanical mixture or fluidized-bed reactor to answer device.Preferably, Gas-phase reactor is at least 0.2 including gas velocity The mechanical agitation fluidized-bed reactor of meter per second.It is understood, therefore, that Gas-phase reactor is (preferably with mechanical agitation Device) fluidized-bed reactor.

Therefore, in a preferred embodiment, first reactor is slurry-phase reactor, such as circulating reactor, and Second reactor and the 3rd reactor are Gas-phase reactor.Therefore for the inventive method, at least three, preferably three polymerizations are anti- Device, i.e. slurry-phase reactor (such as circulating reactor), the first Gas-phase reactor and the second Gas-phase reactor is answered to be connected in series and use. If desired, placing pre-polymerization reactor before slurry-phase reactor.

For example, such as in EP 0 887 379, WO 92/12182, WO 2004/000899, WO 2004/111095, WO 99/24478th, such as being developed (referred to as by Borealis described in WO 99/24479 or the patent documents of WO 00/68315Technology) " circulation type-gas phase " method be preferred multi-stage method.

Another suitable slurry-gas phase method is BasellMethod.

Preferably, it is used in the present invention in the method for preparing heterophasic propylene copolymer as defined above, first reactor, i.e., The condition of slurry-phase reactor, such as circulating reactor can be as follows：

- temperature in the range of 50 DEG C to 110 DEG C, preferably between 60 DEG C to 100 DEG C, more preferably 62 DEG C to 85 DEG C it Between,

- pressure in the range of 20 bars to 80 bars, preferably in 40 bars between 70 bars,

- can hydrogen be added in a manner known per se to control molal weight.

Then, the reactant mixture of first reactor is transferred to second reactor, i.e. Gas-phase reactor, its conditional is excellent Selection of land is as follows：

- temperature in the range of 50 DEG C to 130 DEG C, preferably between 60 DEG C to 100 DEG C, more preferably at 75 DEG C to 95 DEG C Between,

- pressure in the range of 5 bars to 50 bars, preferably in 15 bars between 35 bars,

- can hydrogen be added in a manner known per se to control molal weight.

Condition in 3rd reactor and the 4th reactor is similar to second reactor.

Residence time in three reaction zones can be with difference.

In an embodiment of the method for preparing heterophasic polypropylene composition, in bulk reaction device, such as ring Residence time in flow reactor in the range of 0.1 to 3.5 hour, such as 0.15 to 3.0 hour, in Gas-phase reactor Residence time is usually 0.2 to 6.0 hour, such as 0.5 to 4.0 hour.

If desired, polymerization can in known manner at supercritical conditions in first reactor, i.e., in slurry reaction Carried out in device, such as circulating reactor, and/or carried out in Gas-phase reactor with condensation mode.

Preferably, the method also includes using the prepolymerization step of catalyst system as described below, the catalyst System includes Ziegler-Natta procatalyst, external donor and optional co-catalyst.

In a preferred embodiment, prepolymerization is being dissolved with micro other reactants and optional inert component Propylene liguid is carried out in (i.e. liquid phase mainly includes propylene) in the way of bulk slurry polymerizations.

Prepolymerization generally 10 to 60 DEG C, preferably 15 to 50 DEG C, more preferably carried out at a temperature of 20 to 45 DEG C.

Pressure in pre-polymerization reactor is not crucial, but must be sufficiently high with maintenance reaction mixture as liquid phase.Cause This, pressure can be 20 to 100 bars, such as 30 to 70 bars.

Preferably catalytic component is fully incorporated to prepolymerization step.However, being urged in ingredient of solid catalyst (i) and helping When agent (ii) can feed respectively, only part co-catalyst can be incorporated into prepolymerisation stage, remainder is incorporated into Subsequent polymerization stage.Also, in this case it is necessary to will make to obtain sufficient polymerisation in prepolymerisation stage The co-catalyst of amount is incorporated into prepolymerisation stage.

Other components can also be added in prepolymerisation stage.Therefore, as known in the art, can be in prepolymerization rank Duan Tianjia hydrogen is controlling the molecular weight of prepolymer.In addition it is possible to use antisatic additive come prevent particle be adhering to each other or Adhere on the wall of reactor.

The precise control of prepolymerization conditions and response parameter is within the skill of the art.

According to the present invention, as described above, having obtained out-phase by multistage polymerization method in the presence of catalyst system Polypropene composition.

As described above, having used specific neat lattice in the specific method for preparing heterophasic polypropylene composition as defined above Le-Natta catalyst.

Therefore, Ziegler-Natta catalyst will be described in further detail now.

Catalyst used in the present invention is solid Ziegler-Natta catalyst, and it includes the 4th to 6 race of IUPAC The compound of transition metal (such as titanium), group II metal (such as magnesium) compound and inside donor, wherein inside donor are preferably non-neighboring Phthalic acid compounds, more preferably non-phthalic acid ester, non-O-phthalic still more preferably as described in more detail below The diester of sour dicarboxylic acids.Therefore, catalyst is entirely free of unwanted phthalic compounds.Additionally, solid catalyst is not Containing any outer carrier material, such as silica or MgCl₂, and catalyst is self-supported.

Ziegler-Natta catalyst (ZN-C) can further be limited by its preparation method.

Therefore, Ziegler-Natta catalyst (ZN-C) is preferably obtained by the method for comprising the following steps：

a)

a₁) solution of at least group II metal alkoxide compound (Ax), wherein group II metal alkoxide compound are provided (Ax) it is group II metal compound and product of the monohydric alcohol (A) optionally in liquid organic reactant medium, wherein unitary Alcohol (A) also includes at least one ether moiety in addition to hydroxylic moiety；Or

a₂) solution of at least group II metal alkoxide compound (Ax'), wherein group II metal alkoxide compound are provided (Ax') it is group II metal compound (MC) with the alcohol mixture of monohydric alcohol (A) and the monohydric alcohol (B) of formula ROH optionally organic Product in liquid reaction medium；Or

a₃) mixture of group II metal alkoxide compound (Ax) and group II metal alkoxide compound (Bx) is provided Solution, wherein group II metal alkoxide compound (Bx) are group II metal compound and monohydric alcohol (B) optionally in organic liquor Product in precursor reactant medium；Or

a₄) formula M (OR are provided₁)_n(OR₂)_mX_2-n-mGroup II metal alkoxide compound or group II metal alkoxy chemical combination Thing M (OR₁)_n’X_2-n’With M (OR₂)_m’X_2-m’Mixture solution, wherein M is group II metal, and X is halogen, R₁And R₂It is C₂Extremely C₁₆The different alkyl groups of carbon atom, and 0≤n<2,0≤m<2 and n+m+ (2-n-m)=2, condition is n and m ≠ 0,0<n’≤2 And 0<m’≤2；With

B) solution of step a) is added at least one compound of the 4th to 6 group 4 transition metal, and

C) ingredient of solid catalyst particle is obtained,

With inside donor, the inside donor of preferably non-phthalic acid are added in any step before step c).

It is therefore preferred that inside donor or its precursor are added in the solution of step a).

According to process above, by the heavy of the temperature that uses in depending on physical condition, especially step b) and c) Shallow lake method or emulsion (liquid liquid two-phase system) curing can obtain Ziegler-Natta catalyst.

In both approaches (precipitation or emulsion solidification), its catalyst chemical is identical.

In intermediate processing, solution and at least one transistion metal compound in step b) of step a) are combined, And whole reactant mixture is maintained at least 50 DEG C, is more preferably maintained within the temperature range of 55 to 110 DEG C, more preferably It is maintained in 70 to 100 DEG C of temperature ranges, to ensure that (catalytic component that step c) forms are present sinks completely with solid particle Form sediment.

In emulsion curing, in step b), generally such as from -10 DEG C to less than 50 DEG C, preferably from -5 to The solution of step a) is added at least one transistion metal compound at 30 DEG C of relatively low temperature.In the stirring phase of emulsion Between, -10 are generally kept the temperature to less than 40 DEG C, preferably from -5 to 30 DEG C.The droplet formation of the dispersed phase of the emulsion is lived Property carbon monoxide-olefin polymeric.The temperature for be heated to 70 to 150 DEG C by by emulsion, being preferably 80 to 110 DEG C suitably carries out liquid Solidification (the step c) of drop.

Preferably by the catalyst prepared with emulsion curing in the present invention.

In a preferred embodiment, in step a), using a₂) or a₃) solution, i.e., the solution of (Ax ') or (Ax) and (Bx) mixture solution.

Preferably, group II metal is magnesium.

Enter by by magnesium compound and alcohol as described above (class) in the first step of method for preparing catalyst, step a) Row reaction can prepare alkoxyl magnesium compound (Ax), (Ax ') and (Bx) with original position, or the alkoxyl magnesium compound can be The alkoxyl magnesium compound being manufactured separately, or they can even is that it is commercially available as ready-made alkoxyl magnesium compound And this is used in method for preparing catalyst of the invention.

The illustrated examples of alcohols (A) are the monoether class (glycol monoether) of di-alcohols.Preferred alcohols (A) is C₂Extremely C₄Glycol monoether, wherein ether moiety include 2 to 18 carbon atoms, it is therefore preferable to 4 to 12 carbon atoms.Preferred example is 2- (2- ethyl hexyl oxies) ethanol, butoxy ethanol, 2- hexyloxyethanols and 1,3- propane diols-single-butyl ether, 3- butoxy -2- Propyl alcohol, particularly preferably 2- (2- ethyl hexyl oxies) ethanol and 1,3-PD-single-butyl ether, 3- butoxy -2- propyl alcohol.

It is the C of straight or branched that illustrative unary alcohol (B) has formula ROH, R₆-C₁₀Alkyl residue.Most preferred unitary Alcohol is 2- ethyl -1- hexanols or octanol.

Preferably, it is 8 to be respectively adopted and use mol ratio:1 to 2:1, more preferably 5:1 to 3:1 Bx:Ax or B:A's The mixture or alcohol (A) and the mixture of (B) of alkoxyl magnesium compound (Ax) and (Bx).

Alkoxyl magnesium compound can be alcohol as defined above (class) and be selected from dialkyl magnesium, alkyl alkoxy magnesium, two The product of the magnesium compound of alkoxyl magnesium, Alkoxymagnesium halides and alkyl halide magnesium.Alkyl group can be it is similar or Different C₁-C₂₀Alkyl, preferably C₂-C₁₀Alkyl.Typical alkyl-alkoxy magnesium compound (when employed) is ethyl fourth oxygen Base magnesium, butyl amoxy magnesium, octyl group butoxy magnesium and octyl group octyloxy magnesium.Preferably, using dialkyl magnesium.Most preferred dioxane Base magnesium is butyl octyl magnesium or butyl ethyl magnesium.

It is also possible that in addition to alcohol (A) and alcohol (B), magnesium compound can also be with formula R " (OH)_mPolyalcohol (C) React to obtain described alkoxyl magnesium compound.Preferred polyalcohols (if use) are R " it is straight chain, ring-type or side chain C₂To C₁₀Hydrocarbon residue and m are the alcohols of 2 to 6 integer.

Therefore the alkoxyl magnesium compound of step a) is selected from by dialkoxy magnesium, two aryloxy group magnesium, Alkoxymagnesium halides, virtue The group of epoxide magnesium halide, alkyl alkoxy magnesium, alkoxy aryl magnesium and alkyl-aryloxy magnesium composition.Furthermore, it is possible to using dihalo- Change the mixture of magnesium and dialkoxy magnesium.

There are 5 to 20 carbon atoms, more preferably 5 for preparing the solvent that catalyst of the present invention is used and can be selected from To 12 aromatic and aliphatic straight chains of carbon atom, side chain and ring-type hydro carbons or its mixture.Suitable solvent is included Benzene, toluene, isopropylbenzene, dimethylbenzene, pentane, hexane, heptane, octane and nonane.Hexane class and pentane class are particularly preferred.

Magnesium compound is generally provided as the solution of 10 to 50 weight % in solvent as noted above.It is generally commercially available Mg compounds, especially dialkyl magnesium solution is the solution of 20 to 40 weight % in toluene or heptane.

Reaction for preparing alkoxyl magnesium compound can be carried out in 40 DEG C to 70 DEG C of temperature.According to the Mgization for being used The temperature that compound and alcohol (class) selection are best suitable for.

4th race to the transistion metal compound of the 6th race is preferably titanium compound, most preferably such as TiCl₄Halogenated titanium.

Non- phthalic acid inside donor for preparing the catalyst used in the present invention is preferably chosen from non-neighboring benzene two (2) esters of formic acid carboxylic (two) acids, the ethers of 1,3- bis- and its derivative and mixture.Especially preferred donor be unitary not Two esters of saturated dicarboxylic acid class, especially belong to comprising malonic acid esters, maleic acid esters, succinate compound, citraconate The esters of class, glutaric acid esters, cyclohexene -1,2- dicarboxylic acids esters and benzoates, and its any derivative and/or mixed Compound.Preferred example is for example substituted maleic acid esters and citraconic acid esters, most preferably citraconic acid esters.

In emulsion process, by it is single stirring and be optionally added (other) solvent (class) and additive (such as with ability Known mode is used to promote the formation of emulsion and/or turbulent flow minimum agent (TMA) of stable emulsion and/or emulsifying agent in domain And/or emulsion stabilizer (such as surfactant)) two-phase liquid-liquid system can be formed.Preferably, surfactant is acrylic acid Polymer or methacrylate polymer.Particularly preferably unbranched C₁₂To C₂₀(methyl) esters of acrylic acid, such as gather Methacrylic acid (cetyl) ester and polymethylacrylic acid (octadecyl) ester and their mixture.If using turbulent flow Minimum agent (TMA), it is preferably chosen from having 6 to 20 alpha-olefine polymers of the 'alpha '-olefin monomers of carbon atom, such as poly- pungent Alkene, poly- nonene, poly decene, poly- hendecene or poly- laurylene or their mixture.Most preferably poly decene.

With aromatic hydrocarbon and/or aliphatic hydrocarbon, preferably use toluene, heptane or pentane can be to by precipitation or emulsion The solia particle product that curing is obtained is washed at least one times, preferably at least twice, most preferably at least three times.Such as pass through Evaporation is rinsed and further the catalyst can be dried with nitrogen, or can need not be appointed its pulp for oily liquids What drying steps.

The Ziegler-Natta catalyst for finally giving ideally with usually 5 to 200 μm, be preferably 10 to 100 μm average particle size range particle form exist.Particle is close with low porosity, and with less than 20g/m², it is more excellent Selection of land is less than 10g/m²Surface area.Generally, the amount of titanium is 1 to 6 weight % of carbon monoxide-olefin polymeric, and the amount of magnesium is catalyst group 10 to 20 weight % of compound and the amount of donor are 10 to 40 weight % of carbon monoxide-olefin polymeric.

Disclosed in WO2012/007430, EP2610271, EP261027 and EP2610272 and prepare retouching in detail for catalyst State, they are incorporated herein by reference.

Preferably with aluminum alkyl catalyst and optionally, external donor is used in combination Ziegler-Natta catalyst.

As other components in polymerization of the present invention, external donor is there is preferably.Suitable external donor is included Some silanes, ethers, esters, amine, ketone, heterocyclic compound and their blend.Particularly preferably use silicon Alkane.Most preferably use the silanes of following formula：

R^a _pR^b _qSi(OR^c)_(4-p-q)

Wherein R^a、R^bAnd R^cAlkyl, particularly alkyl group or group of naphthene base are represented, and wherein p and q are from 0 to 3 In the range of numeral and their summation p+q be equal to or less than 3.R^a、R^bAnd R^cCan be selected independently of one another and can phase It is same or different.The specific example of the silanes is (tert-butyl group)₂Si(OCH₃)₂, (cyclohexyl) (methyl) Si (OCH₃)², (phenyl)₂Si(OCH₃)₂(cyclopenta)₂Si(OCH₃)₂Or the silanes with below general formula：

Si(OCH₂CH₃)₃(NR³R⁴)

Wherein R³And R⁴The alkyl with 1 to 12 carbon atom can be represented with identical or different.

R³And R⁴Independently selected from by with 1 to 12 straight chain fatty hydrocarbyl group of carbon atom, with 1 to 12 carbon atom Branched aliphatic hydrocarbons group and the ring-shaped fat hydrocarbyl group composition with 1 to 12 carbon atom group.It is particularly preferred that R³With R⁴Independently selected from methyl, ethyl, n-propyl, normal-butyl, octyl group, decyl, isopropyl, isobutyl group, isopentyl, the tert-butyl group, uncle The group of amyl group, neopentyl, cyclopenta, cyclohexyl, methylcyclopentyl and suberyl composition.

It is highly preferred that R¹And R²Both are identicals, it is more preferred still that R³And R⁴It is ethyl group.

Especially preferred external donor is dicyclopentyl dimethoxyl silane donor (D donors) or cyclohexyl methyl dimethoxy Base silane donor (C donors).

Except Ziegler-Natta catalyst and optional external donor, co-catalyst can also be used.Co-catalyst is preferred Ground is the 13rd compounds of group of periodic table (IUPAC), for example organo-aluminium (such as aluminium compound, as alkyl aluminum, aluminum halide or alkyl halide Change aluminium compound).Therefore, in a specific embodiment, co-catalyst is trialkylaluminium, two such as triethyl aluminum (TEAL) Alkyl aluminum chloride or alkyl al dichloride or its mixture.In a specific embodiment, co-catalyst is triethyl aluminum (TEAL)。

Preferably, the ratio [Co/ED] and/or co-catalyst (Co) between co-catalyst (Co) and external donor (ED) with Ratio [Co/TM] between transition metal (TM) should all carry out well-chosen.

Therefore

A () co-catalyst (Co) must be in the range of 5 to 45, preferably with the mol ratio [Co/ED] of external donor (ED) Ground in the range of 5 to 35, more preferably in the range of 5 to 25；Optionally

B () co-catalyst (Co) must be in the scope more than 80 to 500 with the mol ratio [Co/TC] of titanium compound (TC) It is interior, preferably in the range of 100 to 350, more preferably in the range of 120 to 300.

Heterophasic polypropylene composition of the invention is preferably polymerized in the presence of following material：

A) compound (TC) of the transition metal of the 4th to 6 race including IUPAC, group II metal compound and inside donor Ziegler-Natta catalyst, wherein the inside donor is non-phthalic compounds, preferably non-phthalic acid Ester, and be even more preferably still the diester of non-phthalic acid dicarboxylic acids；

B) optional co-catalyst (Co), and

C) optional external donor (ED).

Preferably, inside donor (ID) is selected from optional substituted malonic acid esters, maleic acid esters, succinate Class, glutaric acid esters, cyclohexene -1,2- dicarboxylic acids esters, benzoates and their derivative and/or mixture, preferably Ground inside donor (ID) is citraconate.Additionally or alternatively, the mol ratio of co-catalyst (Co) and external donor (ED) [Co/ED] is 5 to 45.

If heterophasic polypropylene composition of the invention also includes component (D), α-nucleator, then subsequent out-phase poly- third Ene compositions are by α nucleation.

Reactor last from series reaction device collects heterophasic polypropylene composition, by α-nucleator and optional its Its additive is added in heterophasic polypropylene composition.Combined heterophasic polypropylene is prepared by being combined fraction defined above In the case of thing, any additive can together be added or added after the composite steps in the composite steps.

Preferably, these additives are mixed into composition in the step recombination process before or during extrusion In.Alternatively, masterbatch can be prepared, wherein first only mixing heterophasic polypropylene composition with portions additive.

For mixing, it is possible to use conventional compound or intermingling apparatus, for example, Ban Buli (Banbury) mixer, double roller Rubber grinder, Buss co-kneaders or double screw extruder.Double screw extruder can be with rotating Vortex or reverse rotation, preferably It is rotating Vortex.Preferably, by it is sufficiently high with soften and plasticized polymer at a temperature of by additive and polymeric material It is blended to prepare composition.The temperature and pressure used in the operation of extruder is known in the art.Generally, temperature can be with Selected from 150 to 350 DEG C of scope.Pressure for extruding is preferably 50 to 500 bars.The polymeric material reclaimed from extruder leads to It is often partical.Then preferably these pellets are processed further, such as by injection moulding preparing combination of the present invention The product and product of thing.

It is preferred that by heterophasic polypropylene of the invention combination before or while nucleator and other additives or masterbatch is added Thing carries out above-mentioned optional blending with other polypropylene homopolymer matrix materials (A).

Therefore, in another embodiment, by the heterophasic polypropylene composition for preparing as described above and other polypropylene Homopolymer matrix material (A) is blended.

In this embodiment, the heterophasic polypropylene composition for preparing as described above is referred to as " basic heterophasic polypropylene group Compound (base heterophasic polypropylene composition) ".

The polypropylene homopolymer matrix material (A) that will be obtained after first Gas-phase reactor of such as above-mentioned method is used as jointly Blend, which results in " dilution " of " basic heterophasic polypropylene composition ", it is possible thereby to consider the amount and mechanicalness of XCS Can, by the property for carefully adding other polypropylene homopolymer matrix materials (A) of specified quantitative to optimize XCS fractions.

Preferably, the blend includes 75 to 99 weight %'s, preferably 80 to 95 weight %, more preferably 85 to 93 weight % Other of " basic heterophasic polypropylene composition " and 1.0 to 25 weight %, preferably 5 to 20 weight %, more preferably 7 to 15 weight % Polypropylene homopolymer matrix material (A).

For blending, conventional compound or intermingling apparatus can be reused, such as Ban Buli (Banbury) mixer, Double roller rubber mill, Buss co-kneaders or double screw extruder.Double screw extruder can be with rotating Vortex or reverse rotation, preferably It is rotating Vortex.

The purposes of heterophasic polypropylene composition

Another embodiment of the invention, heterophasic polypropylene composition of the invention and the composition with fill out The combination of material or reinforcing agent be used to preparing membrane product, extruded product, blow molded article or injection molded article (such as pouch and The component of bag, pipe and accessory, transportation package holdses and automobile exterior and interior trim, such as instrument board, door covering, operating desk, insurance Thick stick and decoration) in.

In addition, the invention further relates to by polypropene composition of the invention or the composition and filler or the group of reinforcing agent The product for preparing is closed, especially membrane product, extruded product, blow molded article or injection molded article.

The product by be suitable for thermoplastic polymer any conventional transformation methods (such as injection moulding, extrusion-blown modling into Type, injection stretch blow molding or cast film extrusion) prepare.

If heterophasic polypropylene composition of the invention is used with filler or reagents recombination, based on heterophasic polypropylene The content of composition, described filler or reinforcing agent is less than 30 weight %, preferably shorter than 25 weight %, more preferably less than 22 weights Amount %.

Experimental section

A. assay method

Unless otherwise defined, the definition of following term and assay method are applied to includes claim and following examples Above-mentioned general description of the invention.

Quantization by NMR spectra to micro-structural

Quantitative nuclear magnetic resonance (NMR) composes the quantization of isotacticity and regio-regular degree for the Noblen.

Using right¹H and¹³The nuclear-magnetisms of Bruker Advance III 400 that C is operated under 400.15 and 100.62MHz respectively Resonance spectrometer records quantitative under solution state¹³C{¹H } H NMR spectroscopy.It is used for all pneumatic means, profit using nitrogen at 125 DEG C With¹³The 10mm all spectrum of extended temperature probes records of C optimizations.

For Noblen, the material of about 200mg is dissolved in 1,2- tetrachloroethanes-d₂(TCE-d₂) in.To ensure Uniform solution is obtained, after preparing initial sample in heat block, NMR pipes few 1 is further heated in rotary oven small When.After magnet is inserted, NMR pipes rotate under 10Hz.The setting is selected primarily to needed for isotacticity distribution quantization High-resolution (Busico, V., Cipullo, R., Prog.Polym.Sci.26 (2001) 443；Busico, V； Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules, 30 (1997) 6251).It is logical Cross using NOE and bilayer WALTZ16 decoupling scheme come utilize standard single pulse excitation (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D.Winniford, B., J.Mag.Reson.187 (2007) 225； Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol.Rapid Commun.2007,28,11289).Each spectrum obtains 8192 (8K) transient states altogether.

To quantitative¹³C{¹H } NMR spectra is processed, integrated, and come true from integration using proprietary computer program Determine dependent quantization performance.

For Noblen, all chemical shifts be all with 21.85ppm at the isotactic group of Unit five of methyl (mmmm) as internal reference.

It is observed that corresponding region defect (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem.Rev.2000,100,1253；Wang, W-J., Zhu, S., Macromolecules, 33 (2000), 1157；Cheng, H.N., Macromolecules 17 (1984), 1950) or comonomer characteristic signal.

Steric regularity distribution be quadrature and correct by the methyl region between 23.6-19.7ppm with it is of interest The incoherent any site of three-dimensional sequences and by (Busico, V., Cipullo, R., the Prog.Polym.Sci.26 of quantification (2001)443；Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L., Macromolecules 30(1997)6251)。

Especially, the quantitative influence that area defects and comonomer are distributed to the steric regularity, by from three-dimensional sequence The integration of representative area defect and comonomer is subtracted in the specific integrated area of row to correct.

Isotacticity determines in the level of five unit groups and is reported as isotaxy five unit group (mmmm) sequence Relative to the percentage of all of five single tuple sequences：

[mmmm] %=100* (sums of all groups of Unit five of mmmm/)

The presence of 2,1- erythro form area defects is the presence by two methyl sites at 17.7 and 17.2ppm to be shown And confirmed by other feature sites.Characteristic signal corresponding to other kinds of area defects is not observed (Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253)。

2,1- erythro forms region is quantified using two average integrals in feature methyl site at 17.7 and 17.2ppm to lack Sunken amount：

P_21e=(I_e6+I_e8)/2

Carried out to being included in one's respective area and the incoherent site of main insertion and main insertion point to being excluded from one's respective area Amount of the correction based on methyl region insertion propylene main to 1,2- quantifies：

P₁₂=I_CH3+P_12e

The total amount of propylene is quantification of with the propylene of main insertion and the area defects sum of all other presence：

P_Always=P₁₂+P_21e

The mole percent of 2,1- erythro form area defects is quantified relative to all propylene：

[21e] mole %=100* (P_21e/P_Always)

By NMR spectra to the measure of comonomer

Quantitative nuclear magnetic resonance (NMR) spectrum is used with the co-monomer content and comonomer sequence of quantifying polymers point Cloth.Under solution state using Bruker Advance III 400NMR spectrometers for¹H and¹³C respectively in 400.15MHz and Operated under 100.62MHz quantitative to record¹³C{¹H } NMR spectra.It is used for all pneumatic means, profit using nitrogen at 125 DEG C With¹³The 10mm all spectrum of extended temperature probes records of C optimizations.By the material of about 200mg and chromium acetylacetonate (III) (Cr (acac)₃) together it is dissolved in the 1,2- tetrachloroethanes-d of about 3ml₂(TCE-d₂) in, form 65mM relaxation reagents in a solvent Solution (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475).It is homogeneous to ensure Solution, after preparing initial sample in heat block, NMR pipes is further heated in rotary oven few 1 hour.Insertion magnet Afterwards, pipe rotates under 10Hz.The setting is selected primarily to high-resolution and the quantitative quantization needs of accurate ethylene contents. Standard list is utilized by the tip angle (tip angle) using optimization, the circulation delay of 1s and bilayer WALTZ16 decoupling algorithms Pulse excitation without using NOE (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225；Busico,V.,Carbonniere,P., Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28, 1128).Each spectrum obtains 6144 (6K) individual transient states altogether.

To quantitative¹³C{¹H } H NMR spectroscopy is processed, integrated and to be used proprietary computer program to be determined by integration related Quantitative property.Using the chemical shift of solvent, all chemical shifts are indirectly with reference to ethylene block (EEE) at 30.00ppm Central methylene.Even if there be no this construction unit, this method also allows comparable reference.Can be observed to correspond to second The characteristic signal (Cheng, H.N., Macromolecules 17 (1984), 1950) of the incorporation of alkene.

In the case where the characteristic signal corresponding to 2,1- erythro form area defects is observed (such as in L.Resconi, L.Cavallo, A.Fait, F.Piemontesi, Chem.Rev.2000,100 (4), 1253, Cheng, H.N., Macromolecules 1984,17,1950, and W-J.Wang and S.Zhu, Macromolecules 2000, institute in 33 1157 Description), the correction of influence of the area defects to deterministic nature is by demand.Corresponding to the feature letter of other kinds of area defects Number it is not observed.

¹³C{¹H } in spectrum, by the integration of the multiple signals through whole spectral regions, using Wang et al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) in method quantify comonomer fraction.The method is because of it The sane property and ability of the presence of explanation area defects when needed are chosen.Fine tune integrated area is improving through chance The applicability of the gamut of the co-monomer content for arriving.

For the system that isolated ethene can only be observed in PPEPP sequences, the method for Wang et al. is changed, to reduce Know the influence of the non-zero integral in non-existent those sites.Mistake this approach reduces the ethylene contents to this system is over-evaluated Meter, and realized by reducing the number in the site for determining absolute ethylene contents：

E=0.5 (S β β+S β γ+S β δ+0.5 (S α β+S α γ))

By using the site of this set, corresponding integral equality is changed into：

E=0.5 (I_H+I_G+0.5(I_C+I_D))

Same-sign (Wang, W-J., Zhu, S., Macromolecules employed in article using Wang et al. 33(2000),1157).The equation for absolute propylene content is not changed.

The mole percent of the comonomer for introducing is calculated by molar fraction：

E [mole %]=100*fE

The percetage by weight of the comonomer for introducing is calculated by molar fraction：

E [weight %]=100* (fE*28.06)/((fE*28.06)+((1-fE) * 42.08))

Using Kakugo et al. analysis method (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T.Macromolecules 15 (1982) 1150) determine the comonomer sequence distribution in three unit group levels.The selection party Method is due to its sane property and somewhat adjustment integral domain to increase the applicability of the co-monomer content of wider range.

Xylene soluble part fraction (XCS, weight %) at room temperature：The amount of polymer of dimethylbenzene is dissolved at 25 DEG C It is lower according to ISO 16152；5th edition；2005-07-01 determines.

Inherent viscosity (iV)

Inherent viscosity (V) value increases with polymer molecular weight.The iV values of such as XCS are existed according to ISO 1628/1 Measured in naphthalane at 135 DEG C.

Dsc analysis, melt temperature (T_m), melting enthalpy (H_m), crystallization temperature (T_c) and crystallization enthalpy (H_c)：With TAInstrument Q200 differential scanning calorimetries (DSC) are measured on the sample of 5 to 7mg.DSC is according to ISO 11357/ third portion/method C2 is under the circulation of heating/cooling/heating with the sweep speed of 10 DEG C/min in -30 to+225 DEG C of temperature Run in the range of degree.Crystallization temperature (T is determined from cooling step respectively_c) and crystallization enthalpy (H_c), from the second heating stepses ( In the case of net from the first heating stepses) determine melt temperature (T_m) and melting enthalpy (H_m)。

Glass transition temperature Tg is determined by according to the dynamic mechanics heat analysis of ISO 6721-7.The measurement is to reverse To compression molded samples (40 × 10 × 1mm between -100 DEG C and+150 DEG C under pattern³) with the rate of heat addition of 2 DEG C/min and 1Hz Frequency is carried out.

MFR₂(230 DEG C) are come what is determined according to ISO 1133 (230 DEG C, 2.16kg loads).

Melt flow rate (MFR) is determined to polypropylene according to ISO 113315 (230 DEG C, 2.16kg loads), according to ISO1133 (190 DEG C, 2.16kg loads) determine melt flows speed to polyethylene, and are represented with g/10min.MFR characterizes polymer flowability, Thus the processability of polymer is characterized.Melt flow rate (MFR) is higher, and the viscosity of polymer is lower.

Calculated using the MFR2 values of the mixture (" final ") obtained by the fraction (A) and preparation fraction (B) afterwards for being determined The MFR2 of the fraction (B) prepared in the presence of fraction (A)：

Log(MFR_Finally)=weight fraction (A) * Log (MFR_A)+weight fraction (B) * Log (WFR_B)

Volatile matter total release

By using according to VDA 277:1995 multiple headspace extractions, polymerization is determined using gas-chromatography and Head space The total release of thing.Equipment is equipped with 30m WCOT long and 0.25 millimeter × 2.5 micron inside diameters (0.25 micron film thickness) The Hewlett Packard gas chromatographs of capillary column (paraffin wax type).Use the flame ion using hydrogen as fuel gas Detector.

GC settings are as follows：In 50 DEG C of isothermals 3 minutes, 200 DEG C are warming up to 12K/min, in 200 DEG C of isothermals 4 minutes, injection Temperature：200 DEG C, detection temperature：250 DEG C, carrier gas is helium, stream mode shunting 1:20 and average carrier gas speed is 22 to 27cm/ s。

After the gas chromatographic analysis of calibration standard and flame ion detection is used acetone as, by emission of substance institute On the basis of the summation of all values of offer, potential emission amount is determined.After controlling to carry out 5 hours at 120 DEG C before testing, pass through Headspace analysis (10ml headspace vials) introduces sample (pellet, about 1 gram).

Unit is μ gC/g (every gram of sample μ g carbon), respectively in terms of ppm.

Shrinkage factor

Meet the 150 of ISO 1873 by the way that resin injection (mo(u)lding) machine to be injection molded to be formed in the mould with cavity ×80×2mm³Plate determine shrinkage factor.After being cooled to room temperature 96 hours, the length and width of the plate is determined, calculated with hundred The shrinkage factor of the vertical and horizontal of fraction representation.

Simply supported beam notch impact strength

Simply supported beam notch impact strength is used according to the notes of ISO 1873 at 23 DEG C and -20 DEG C according to the 1eA of ISO 179 Penetrate test sample (80 × 10 × 4mm) measure of shaping.

Bending modulus：Bending modulus is according to ISO 178 using meeting EN ISO 1873-2 injection molding 80 at 23 DEG C ×10×4mm³Measured with three-point bending in test-strips.

Stretch modulus：

Using note being prepared according to EN ISO1873-2, being molded at 180 DEG C or 200 DEG C according to ISO 527-2 (1B) Penetrate shaping sample (bone-shaped of dog 10,4mm are thick) and stretching is measured according to ISO 527-1 (crosshead speed 1mm/min) at 23 DEG C Modulus.

Powder flowbility：

Powder flowbility is with according to ISO 6186:The powder flowbility experiment of 1998, method A is determined.

B. example

For the system of the catalyst in the polymerization of the heterophasic polypropylene composition of example of the present invention (IE 1 to IE 5) It is standby as follows：

Chemicals used：

20% butyl ethyl magnesium (Mg (Bu) (Et), BEM) toluene solution, is provided by Chemtura

2-Ethylhexyl Alcohol, is provided by Amphochem

3- butoxy -2- propyl alcohol-(DOWANOL^TMPnB), provided by Dow

Citraconic acid two (2- ethylhexyls) ester, is provided by SynphaBase

TiCl₄, provided by Millenium Chemicals

Toluene, is provided by Aspokem

1-254, is provided by Evonik

Heptane, is provided by Chevron

The preparation of alkoxyl magnesium compound

In 20 liters of stainless steel reactors, in the case where (70rpm) is stirred, alkoxyl magnesium solution is by the 20 weight % to 11kg Butyl ethyl magnesium (Mg (Bu) (Et)) toluene solution in add the mixed of 4.7kg 2-Ethylhexyl Alcohols and 1.2kg butoxypropanols Compound and prepare.In adition process, reactor content is maintained at less than 45 DEG C.After the completion of addition, by reactant mixture Continue to mix (70rpm) 30 minutes at 60 DEG C.After being cooled to room temperature, by the donor citraconic acid two (2- ethylhexyls) of 2.3kg Ester is added to temperature and is maintained in the alkoxyl magnesium solution less than 25 DEG C.Continue to mix 15 minutes in the case where (70rpm) is stirred.

The preparation of ingredient of solid catalyst

By 20.3kg TiCl₄It is added in 20 liters of stainless steel reactors with 1.1kg toluene.Mix under 350rpm and incite somebody to action Temperature is maintained at 0 DEG C, the alkoxyl magnesium compound prepared in adding 14.5kg examples 1 in 1.5 hours.Add 1.7 litersThe heptane of 1-254 and 7.5kg, and at 0 DEG C after mixing 1 hour, will form the temperature of emulsion in 1 hour It is increased to 90 DEG C.Stop mixing after 30 minutes, catalyst droplets are cured so that the catalyst granules sedimentation for being formed.Sedimentation After (1 hour), supernatant is siphoned off.Then catalyst granules is washed 20 minutes with 45kg toluene at 90 DEG C, then uses heptan Alkane is washed twice (30kg, 15 minutes).During first time heptane wash, temperature is reduced to 50 DEG C, and is washed for the second time Room temperature is down to during washing.

Using thus obtained catalyst and the triethyl aluminum (TEAL) as co-catalyst and the two (rings penta as donor Base) dimethoxysilane (D- donors) is used together.

The mol ratio [Co/ED] and co-catalyst (Co) and titanium compound (TC) of co-catalyst (Co) and external donor (ED) Mol ratio [Co/TC] be shown in Table 1.

It is polymerized in Borstar pilot-plants, the device includes pre-polymerization reactor, circulating reactor and two Or three Gas-phase reactor.Polymerizing condition is also depicted in table 1.

Table 1:The polymerization of example of the present invention

The property of the product obtained from each reactor is naturally not on homogeneous material but in reactor sample (office Portion's sample) on measure.The property of final resin is measured on the material of homogeneous, the MFR of the pellet for thus preparing₂As follows Measured during described extrusion mixing.

For example of the present invention 6, the polymer that will be obtained in example 2 as " basic heterophasic polypropylene composition ", then It is blended.

Using propylene homopolymer matrix polymer (PP-H) as common blend, propylene homopolymer matrix polymer (PP- H) in prepolymerization circulating reactor (R1) and a GPR (R2), under the above-mentioned polymerizing condition of example 2, above-mentioned catalysis is used Agent is prepared.

Table 2:Common blend Noblen (PP-H)

Example 6：" basic heterophasic polypropylene composition " (example 2) and 10 weight % Noblens containing 90 weight % (PP-H) blend

It is blended in the Coperion W＆P ZSK40 double screw extruders within the temperature range of 220 to 240 DEG C and addition Agent hybrid combining is carried out.

For the additive used by all resins：Four (3- (the tertiary fourths of 3', 5'- bis- of the 0.1 weight % provided by BASF AG Base -4- hydroxy phenyls)-propionate (CAS 6683-19-8, trade name Irganox 1010), carried by BASF AG Tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester (the CAS 31570-04-4,10 Irgafos of commodity of the 0.1 weight % for supplying 168) calcium stearate (CAS 1592-23-0) of the 0.05 weight % for and by Croda Polymer Additives providing.

For comparative example CE1 and CE2, heterophasic polypropylene polymer below proceeds as described below preparation：

Comparative example CE1

The ZN104 commercially available from Basell is used in CE1.

Comparative example CE2 and CE3

The preparation of the catalyst of CE2 and CE3

First, under atmospheric pressure, 0.1 mole of MgCl₂× 3EtOH is suspended in reactor under inert conditions In the decane of 250ml.Solution is cooled to -15 DEG C of temperature and the cold TiCl of 300ml is added₄, while keeping temperature is in institute State level.Then, the temperature of slurry is slowly raised to 20 DEG C.At this temperature, to the adjacent benzene that 0.02 mole is added in slurry Diformazan dioctyl phthalate (DOP).After phthalic acid ester is added, temperature is increased to 135 DEG C in 90 minutes, slurry is stood 60 minutes.Then, the TiCl of other 300ml is added₄And temperature is kept for 120 minutes at 135 DEG C.Hereafter, catalyst is from liquid Filtered in body, and 300ml heptane wash is used six times at 80 DEG C.Then, ingredient of solid catalyst is filtered and is dried.

Generally described in such as patent document EP 491 566, EP 591 224 and EP 586 390 catalyst and its Prepare concept.

Further the catalyst is modified (VCH of catalyst is modified).

At room temperature, 35ml mineral oil (Paraffinum Liquidum PL68) is added under inert conditions In 125ml stainless steel reactors, be subsequently adding 0.82g triethyl aluminums (TEAL) and 0.33g dicyclopentyl dimethoxyl silanes (to Body D).After 10 minutes, 5.0g catalyst produced above (Ti contents are 1.4 weight %) is added, added after 20 minutes in addition 5.0g vinyl cyclohexanes (VCH).In 30 minutes by temperature rise to 60 DEG C and keep 20 hours.Finally, 20 are cooled the temperature to DEG C, and analyze unreacted VCH concentration in oil/catalyst mixture, it is found that it is 200 weight ppm.

It is used for CE1 and CE2 using two (cyclopenta) dimethoxysilane (donor D) as external donor.

Comparative example CE4：

Using with CE2 identicals catalyst (referring to the preparation of above-mentioned catalyst), unlike the catalyst not enter advance One step it is modified (catalyst does not carry out VCH and is modified).

Comparative example CE5：

By using the catalyst for example 1 and example 2, contrast is prepared in four reactors that such as example 2 is set Example 5CE5.

Table 3+4:The polymerization of comparative example CE1, CE2, CE3, CE4 and CE5

Table 4:The polymerization of comparative example CE2, CE3, CE4 and CE5

Comparative example CE6 and CE7 are blends.

In order to prepare blend, the polymer that will be obtained in example 2 then will as " basic heterophasic polypropylene composition " It is blended.

Using propylene homopolymer matrix polymer (PP-H) as common blend, propylene homopolymer matrix polymer (PP- H) in prepolymerization circulating reactor (R1) and a GPR (R2), under the above-mentioned polymerizing condition of example 2, above-mentioned catalysis is used Agent is prepared.(condition is as shown in table 2)

CE6：Comprising 40 weight % " basic heterophasic polypropylene composition " (example 2) and 60 weight % Noblens (PP- H blend)

CE7：Comprising 20 weight % " basic heterophasic polypropylene composition " (example 2) and 80 weight % Noblens (PP- H blend)

The polymer of comparative example 8 is in prepolymerization circulating reactor (R1) and a GPR (R2), in the upper of example 2 State under polymerizing condition, the propylene homopolymer matrix polymer (PP-H) being prepared with above-mentioned catalyst.(the condition such as institute of table 2 Show).

The property of the product obtained from each reactor is naturally not on homogeneous material but in reactor sample (office Portion's sample) on measure.The property of final resin is measured on the material of homogeneous, the MFR of the pellet for thus preparing₂Such as Measured during lower described extrusion mixing.

All resins are mixed in double screw extruder using following additive：0.1 weight provided by BASF AG Measure four (3- (3', 5'- di-tert-butyl-hydroxy phenyl)-propionates (the CAS 6683-19-8, trade name of % Irganox1010), tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester (the CAS 31570- of the 0.1 weight % for being provided by BASF AG 04-4,10 Irgafos 168 of commodity) and by Croda Polymer Additives provide 0.05 weight % stearic acid Calcium (CAS 1592-23-0).

The property of polymer is put into table 5 and table 6：

Table 5:The polymer property of example (example 1 to example 6) of the present invention

Normalized PEP (XCS)=I (E)

Table 6:The polymer property of comparative example CE1 to CE8

From table 5 and table 6

From table 5 and 6 it can be clearly seen that compared with comparative example, heterophasic polypropylene composition of the invention has comparable Powder flowbility high, reduce discharge capacity and relatively low shrinkage factor, maintain favourable impact strength/rigid balancing.

This can also from Fig. 1 related to example 1 and CE1 and CE5 and from Fig. 2 to Fig. 4 in find out.

Claims

1. a kind of heterophasic polypropylene composition, including：

(A) the crystalline isotactic propylene homopolymer matrix of 48 to 78 weight %, it has and passes through¹³C-NMR is spectrometric big In 96 moles of % five unit group concentration and according to ISO 1133 determined under 230 DEG C and 2.16kg loads in 15 to 200g/ Matrix melt flow rate (MFR) (MFR in the range of 10min_M),

(B) the predominantly unbodied propylene copolymer of 22 to 52 weight %, it has the ethene and/or tool of 25 to 48 weight % There are 4 to 10 alpha-olefins of carbon atom, be present in the composition as scattered particle, and

(C) crystalline ethylene copolymer of 0.0 to 5.0 weight %, it has 3 to 10 alpha-olefins of carbon atom, used as dividing for (B) The field trash of scattered seed is present in the composition, and

The composition is further characterized in that

The total melt flow determined under 230 DEG C and 2.16kg loads according to ISO 1133 in the range of (i) 2.0 to 50g/10min Dynamic speed (MFR_T),

(iii) the XCS fractions determined in 135 DEG C of naphthalane according to DIN ISO 1628/1 in the range of 2.5 to 9.0dl/g Inherent viscosity, and

(iv) relative amount (I (E)) of the isolated ethene sequence pair block ethylene sequence of the XCS fractions of inequality (I) is met

I(E)<78–1.97×C+0.015×(C)²

Wherein C is the co-monomer content [weight %] of the XCS fractions

Wherein I (E) contents by etc. formula (II) defined,

I (E) = \frac{f P E P}{(f E E E + f P E E + f P E P)} \times 100 - - - (I I)

Wherein

FPEE is the molar fraction of propylene/ethylene/ethene sequence (PEE) and ethylene/vinyl/propylene sequences (EEP) in sample；

FEEE is the molar fraction of ethylene/vinyl/ethene sequence (EEE) in sample；

The concentration of wherein all sequences is all based on¹³The unit group analysis of statistics three of C-NMR data.

2. heterophasic polypropylene composition according to claim 1, wherein, MFR_T/MFR_MRatio≤0.5.

3. heterophasic polypropylene composition according to claim 1 and 2, it includes the root for having in the range of 160 to 170 DEG C According to the fusing point (T of the dsc analysis of ISO 11357_m) crystalline polypropylene composition, and optionally have in 105 to 130 DEG C of scope The crystalline polyethylene composition of the fusing point of the interior dsc analysis according to ISO 11357.

4. the heterophasic polypropylene composition according to claim 1,2 or 3, it is characterised in that in 500 to 1100MPa scopes It is interior in 80 × 10 × 4mm³Injection moulding sample on according to ISO 178 measure bending modulus (FM) or 500 to The stretch modulus (TM) measured at 23 DEG C according to ISO 527-1 (crosshead speed 1mm/min) in the range of 1100MPa and In addition it is at least 10.0kJ/m²In 80 × 10 × 4mm³Injection moulding sample at 23 DEG C according to ISO 1791eA determine Simply supported beam notch impact strength (NIS).

5. heterophasic polypropylene composition according to any one of claim 1 to 4, it has in 6.0 to 26.0 weight % In the range of definition be ethene and 4 to 10 total comonomer contents of the content sum of the alpha-olefin of carbon atom.

6. heterophasic polypropylene composition according to any one of claim 1 to 5, it is characterised in that by according to ISO At least two glass transition point (the T that the dynamic mechanical analysis of 6721-7 are determined_g), wherein equal with crystalline isotactic propylene A relevant T of copolymer matrix_g(Tg (1)) is relevant with predominantly unbodied propylene copolymer in the range of -4 to 4 DEG C Another T_g(Tg (2)) are in the range of -60 to -35 DEG C.

7. heterophasic polypropylene composition according to any one of claim 1 to 6, it is characterised in that in 4.5 to 35kJ/m³ In the range of in 80 × 10 × 4mm³Injection moulding sample at -20 DEG C according to the 1eA of ISO 179 measure simply supported beam lack Mouth impact strength.

8. heterophasic polypropylene composition according to any one of claim 1 to 7, it is characterised in that the basis less than 20 seconds ISO 6186：The powder flowbility that 1998, method A are determined, less than 25ppm according to VDA 277:1995 volatile matters for determining Total release, the longitudinal contraction rate that the method described in the basis " assay method explanation " less than 1.2% is determined.

9. heterophasic polypropylene composition according to any one of claim 1 to 8, including being less than based on the composition The filler or reinforcing agent of the amount of 30 weight %.

10. heterophasic polypropylene composition according to any one of claim 1 to 9, wherein the composition is following It is polymerized in the presence of material：

A) compound (TC) of the transition metal of the 4th to 6 race including IUPAC, group II metal compound (MC) and inside donor (ID) Ziegler-Natta catalyst (ZN-C), wherein the inside donor (ID) is non-phthalic compounds, preferably It is non-phthalic acid ester；

B) co-catalyst (Co), and

C) optionally external donor (ED).

11. heterophasic polypropylene compositions according to claim 10, wherein the inside donor (ID) is selected from includes the third two Esters of gallic acid, maleic acid esters, succinate compound, citraconic acid esters, glutaric acid esters, cyclohexene -1,2- dicarboxylic acids esters and benzene Formate ester and it is any they derivative and/or mixture group.

The 12. heterophasic polypropylene composition according to claim 10 or 11, wherein co-catalyst (Co) and external donor (ED) mol ratio [Co/ED] in the range of 5 to 45, the mol ratio [Co/TC] of co-catalyst (Co) and titanium compound (TC) In the range of more than 80 to 500.

13. it is a kind of for being polymerized with ethene and/or the method for propylene that is combined of the alpha-olefin with 4 to 10 carbon atoms, Carried out in the reactor of more than three and in the presence of following material, to obtain according to any one of claim 1 to 9 Heterophasic polypropylene composition：

B) co-catalyst (Co), and

C) optionally external donor (ED).

14. methods for polypropylene according to claim 13, wherein the inside donor (ID) is selected from optionally taking The malonic acid esters in generation, maleic acid esters, succinate compound, glutaric acid esters, cyclohexene -1,2- dicarboxylic acids esters, benzoic acid Esters and their derivative and/or mixture, the preferred inside donor (ID) is citraconate.

A kind of 15. methods for preparing heterophasic polypropylene composition according to any one of claim 1 to 9, use The pre-polymerization reactor (I) of series connection, a fluid bulk reactor (II) and two or more Gas-phase reactor (III), (IV) and Optional (IV), is carried out in the presence of following material：

B) co-catalyst (Co), and

C) optionally external donor (ED),

Wherein polypropylene homopolymer is prepared in the fluid bulk reactor (II) and subsequent the first Gas-phase reactor (III) Matrix (A), then prepares the propylene copolymer in the second Gas-phase reactor (IV) and the 4th optional Gas-phase reactor (V) (B), obtain heterophasic polypropylene composition according to any one of claim 1 to 8 or

" basic heterophasic polypropylene composition " is obtained, by it with based on " the basic heterophasic polypropylene composition " 1.0 to 40 Other polypropylene homopolymers obtained in fluid bulk reactor (II) and subsequent the first Gas-phase reactor (III) of weight % Matrix is blended, and obtains heterophasic polypropylene composition according to any one of claim 1 to 9.

16. prolylene polymer compositions according to any one of claim 1 to 9 are producing membrane product, extruded product, are blowing Purposes in modeling moulded products or injection molded article.

A kind of 17. membrane products, extruded product, blow molded article or injection molded article, including according in claim 1 to 9 Prolylene polymer composition described in any one.